Method for making colored crepe paper with insoluble dyes and resulting product



Apnl 29, 1930. G. R. ALDEN 1,756,778

METHOD FOR MAKING COLORED CREPE PAPER WITH INSOLUBLE DYES AND RESULTING PRODUCT Filed Nov. 12, 1926 Irpve 71/1507 li-wrdvzer'. M5! 71/ Patented Apr. ,29, 1930 UNITED STATE? r "1* OFFICE MANUFACTURING GOMIANY, OF FRAMING :s

OF MASSACHUSETTS H7: IEAQSACHUSETTS, A. CORPORATION METHOD FOR MAKING COLORED CREE-E PAPER WITH INSQLUBLE D'YES RESULTING PRODUCT Application filed November 1%, 1926. Serial-No. 147,969.

This invention relates to a method for the manufacture of non-bleeding colored crepe sheet of suitable paper wlth a dye solution and with a fixing solution, successively or simultaneously, and then creping the this I dyed sheet as by passing it through the usual creping bath and over a creping roll. In this course of procedure there are certain limitations and disadvantages which may 8.1188' 1n the course of practical operations which it is desirable to overcome or avoid. For example, in such processessome fixing reagents,- such as alumlnum sulfate or the like, cause the precipitation of the adhesive which it is rovide in t e creping.

often desirable to bath), thus destroy1ng it for further use. Moreover, the adhesive and some fixing agents or dyes tend to accumulate upon the creping roll and interfere with the proper creping operation," forming streaks or lines in the paper, and thus finally necessitate a thorough cleaning of this part of the machine. This is especially likely to occur when the creping roll is heated. Again, certain reagents (such as tannic acid and inorganic salts) may react with and corrode the surface: of the iron creping roll. This makes it necessary to remove and regrind the roll to ob-'- cur, may be avoided and to produce a satisfactory non-bleeding colored crepe aper.

Other objects will appear from the disc osu e and claims.

The method of the invention includes generally the treatment of asheet of paper with the dye solution or the fixing agent or such other reagent materials as may not deleteriously affect the crepin bath or creping operatiomthen creping t e sheet, and subsequently applying to the creped sheet such active reagent materials as may be required and in such a manner as substantially to preservethe creped structure'of the sheet.

For example, a sheet of paper ma be first treated with a dye solution inert wit respect to the crepini then creped, wit-h or without the use of adhesive) and t e dyed and cre ed sheet then treated with the appropriate xing or other reagents. In such cases the dye solution ma serve also as a creping bath and if desiretz a suitable adhesivemay be added thereto or a separate creping bath may be employed.v

A further improvement in the method may be effected by dissolving the fixing reagent (especially when applied after the creping operation) in such a solvent or in such concentration that it does not seriously afiect or reduce the crepe of the sheet. On the other hand, the ,paper may first be treated with the fixing reagent (where the fixin reagent may be added to or contacted wit the creping bath without detriment) and the paper then creped, and the creped paper subsequently treated with an appropriate dye solution.

A specific and representatlve instanceof the application of the invention will now be described as carried out by' means of the apparatus illustrated in the accompanying drawings in which- The figure is a diagrammatic side elevation of the several pieces of apparatus required. Referring to the drawings, numeral -1 indicates a roll of the paper to be treated,

which is carried upon a roller 2 rotatably bath and creping apparatus,

mounted at 3. The creping apparatus 4 in-' cludes a guide roller 5, a fl ng bar 6, a rubber roller 7, which dips into the solution 8 contained in tank 9. Above roller 7 and in pressure contact therewith is provided a crepmg roll 10 rotatably mounted and having a doctor blade'll in close contact with its eritpheral surface at the desired off-take point 0 the roll. An air nozzle or blower 12 is also positioned adjacent to the" roll between the points of contact with roller 7 and with the doctor blade 11.

- The means for impartlng the subsequent treatment to the creped sheet (whether dye solution or fixing reagent) comprises a flooding bar or roller 13, a pair of compression rollers, including a lower roller 14 (which may have a felted or other resilient and/or irregular surface), dipping into the solution15 in tank 16, and an upper roller 17 which may or may not apply a treating solution, as desired. This apparatus is followed by suitable drying apparatus, if necessary, and a rewinder or other gathering apparatus, not shown.

Appropriate dye solutions for use in the operation of the method may be prepared as follows:

1. For red: Erie fast scarlet 4 BA (Color Index #326-Schultz #279) 5 lbs., water 60 gallons.

2. For orange: pheno orange 0 (Color Index #621-Schultz #11) 5 lbs., water 60 gallons.

3. For orange: auramine (concentrated) (Color Index #655Schultzf #493) 32 ounces, rhodamine 6 GDN ex (Color Index #7 52-Schultz #571) a xanthine basic dye,

' 14 ounces, water 60 gallons.

4. For green: auramine (concentrated) (Color Index #655-Schultz #493) ounces, methylene blue (Color Index #922- Schultz #659) 80 ounces, water 60 gallons.

The adhesive used for facilitating and improvingthecreping operation (if any) may be glue dextrine or the, like and may be dissolved in the dye or in the fixing reagent solution or, as noted above, employed independently.

' tions 1 and 2 above mentloned) may consist,

or An active fixing agent (as for the dye solufor example, of an aqueous solution of alumlnum sulfate. Owing to the wetting and decreping effect of water, it is desirable, as later explained, to use a concentrated solution, whenever it is applied to paper which has been previously creped. To this end a concentrated solution. of ammonium sulfate may be added thereto. Thus a solution containing both15 lbs. aluminum sulfate, 180 lbs. ammonium sulfate, 60 gal. of waterhas been found well suited for the purpose. The two salts may, however, be contained in separate solutions, the concentrated ammonium sulfate solution being applied in the form of a spray, for exam le, and the aluminum sulfate solution (pre erably though not necessarily concentrated) by means of the roller 14 or other device. The presence of the second salt may serve the additional function of fireproofin the sheet.

Preliminary to t e operation of the apparatus, the sheet l is drawn from roller 2 and passed over guide roller 5, beneath flooding bar 6 and over roller 7, between roller 7 and creping roll 10, over the surface of the creping roll to the doctor blade 11, from which it is carried under flooding bar or roller 13 and between the felted rollers 14, 17, and

thence to the drying and take-up mechanism. The sheet may e drawn through the apparatus, but since this tends to stretch and remove the crepe effect, it is preferable to positively drive the several rollers in unison with each other, in the directions indicated by the arrows.

With the apparatus thus arranged, the dye solution, for example, such as that indicated by the first formula above given, is run into the tank 9, together with the adhesive if such is to be used. As already pointed out the dye solution may be separately applied to the sheet first and the sheet then passed through a creping solution in tank 9, but unless intermediate dr ing is resorted to, the dye and lue should e mutually inert in this order 0 procedure. (given above) is then placed in tank 16, or

the alum solution only, and means provided (not shown) for spraying the ammonium sulfate solution upon the top of the sheet or upon roller 17.

The sheet of paper is now passed by rotation of the several rollers under a pool of the dye solution, which is carried upon its upper surface in the depression formed by the flooding bar 6, and distributed-throughout the width of the sheet by the transverse contact of the bar. As the sheet proceeds and comes into contact with the surface of'roller 7 (which is wet with the dye solution) it is wet upon its undersurface, and as the'sheet The fixing solution continues to pass between roller 7 and crep-- ing roll 10 it is firmly compressed and squeezed. This not only completes the uniform distribution of the solution throughout the sheet,-both laterally and transversely through the'sheet, but effectively expresses the surplus of the dye solution which thereupon passes through the sheet and flows down upon its upper surface and maintains the pool of dye solution adjacent to the fiooding bar. The sheet is also thereby brought into intimate contact with the creping roll to which it firmly adheres until it reaches the a more firmly the sheet adheres to the roll, the

more numerous and closely packed the folds of the crepe may be made, and the finer the creping produced. It is also possible to proa given lengthof the sheet bears to the length of the creped sheet resulting therefrom.

The creped sheet may be removed at this point and dried, if desired," and the subsequent treatment independently conducted at a later time, or it may pass directly and continuously to such treatment. In either case, the creped sheet, already colored is next subjected to the fixing treatment. For example, the sheet of crepe paper is passed under a pool of the solution held by flooding bar 13 and thence between the rollers 14 and 17. The lower roller dips intothebath of reagent 15 is thoroughly wet thereby. and carries the solution up and applies it to the under surface of'the creped sheet as it comes into contact therewith and distributes it more uniformly thereover as the paper passes under. compression between the rolls.

While the wetting of crepe paper stock with water or dilute aqueous solutions always re duces the drops ratio to a considerable extent or almost entirely destroys the creped structure, it is found that with concentrated solutlons of certain inorganic electrolytes (for example, salts suoh as ammonium sulfate, sodium nitrate, sodium chloride, sodium sulfate, which are substantially neutral with respect to paper, to prevent deterioration of the sheet) this eflect is practically negligible.

Again, organic solvents have little or, no destructive effect upon crepe paper and some organic l1 ulds, such as alcohol, may contam as muc 1 as of water and stlll remain inefi'ective toward the creped structure of a paper sheet. Accordingly, in any specific instance it is practicable to impart an initial crepe ratio to the paper of such an order that even though a part may be lost by the subsequent treatments. indicated, there will be left a suficient high degree of c reping in the finished sheet to be entirely satisfactory for the desired purpose. 1

Accordingly, to this end, the amount of fixing reagent solution applied to the sheet is kept low and a relatively high concentration of neutral salt is desirable. With such procedure, the crepe of the sheet is not destroyed, nor is itseriously affected, although the solution penetrates the sheet and fixes the dye within the paper fibers, thereby rendering it substantially protected from and relatively insoluble or non-bleeding toward subsequent wetting or other forms of moisture which may come into contact with the sheet.

Moreover, if certain inorganic salts are added to or with the fixing reagent, thereb increasing the effective concentration (sum as ammonium sulfate in the example cited), the paper is simultaneously rendered slowburning or fireproof which is an obvious advantage and secured incidentall to the required operations of dying and xing.

contemplated'that. the fixing reagent may be applied, per se, in an'anhydrous condition, as by dissolving in a strictly anhydrous solvent, i. e. GU1 or C H Katanol (By) is a yellowish powder, soluble in hot water with addition of'sodium carbonate, and possesses a direct affinity for cotton. 10 parts of sulphur are added to a solution of 26 parts of O-chlorophenol in 20 parts of, hot water and 8.5 parts of sodium hydioxide. The mixture is heated immediately to C. under a reflux, and is boiledfor 30 hours. The resinous product which separates is dissolvedin 200 parts of water and 15 arts of soda, reprecipitated with sodium sulp ate, filtered and the greenish paste is dried in vacuo (Fr. Bayer & Co. E. P. 173313; cf., E. 1 .22417 /95, U. S. P. 603755, G. P. 102897;

Guenther, Textilber, 1922,, 209; cf;, J. S. l). C.

1922, 38, 253; Wagner, Farben-Zeit. 1922, 27, 3015).Color Index, 1924, page 357.

As a modification of the application of the invention, as where the dye solution tends to corrode or accumulate uponthe creping rolls, the fixing reagent may be applied to the paper first, followed by creping'the paper and applying the dye .solutionto the treated crepe paper thus produced. This may be effectuated in practice by supplying the solution of fixing reagent to tank 9 and a solution of the dye to tank 16. a In thisorder of operations, an ammoniacal solution of Katanol may be used as the fixing reagent in conjunction with a suitable amount of adhesive (and sodium tungstate, if desired, which serves as a fireproofing agent). The treated sheet is then creped and the dye solution (according to formula three or four given above) may then be applied to the creped sheet already containing the fixing reagent, with or without intermediate drying of the sheet, as required by the conditions of operation.

Accordingly, if t e dye solution is applied first, the fixing rea ent may be applied later, while if the fixing reagent is applied first, the treatment with the dye solution may be postponed and applied later to the impregnated creped sheet, as desired. In other words, by employing a suitable dye or fixing solution (with suhstantially no decreping effeet) in accordance with the present-invention, a creped sheet of papermay be treated nearly as readily and effectively as the plain sheet before creping and the specific sequence of stepsrequiredby other methods (in which the crepingis effected last) need not be adhered to. This results in greater flexibility and the ready adaptation of the process to the practical requirements of manufacture and hence facilitates control of the product and of'the operation of the method at the several sta es-of procedure. y

The product is characterized by having a uniformity of color and of crepe effect and may be of substantially any predetermined shade or 'tone desired. The lustre of the surface, which may be enhanced by using a paper having a finished surface on one or both sides is, to an appreciable degree, preserved.- This is especially noticeable when an organic solvent is used for the fixing reagent. Again, a fine or coarse degree of creping may be imparted to the sheet as de-1 sired, and a high crepe ratio may be obtained and preserved because the subsequent treatment does not seriously impair the crepe finish. Moreover, the finished product is nonbleeding and the colors are relatively fast when brought into contact with moisture or evenwhen thoroughly saturated and soaked with water.

It is apparent that numerous modifications and adaptations of the invention may be made in its practical application and that va rious substitutions and combinations of the raw materials and reagents used. may and ordinarily will be required for specific purposes of manufacture and use. Such modifications and substitutions are, however, to be considered as'comprehended by the foregoing disclosure and included within the following claims.

I claim: i 1. A method for treating colored crepe paper, which comprises treating a sheet of t e same with a concentrated solution of a solid the same between a pair 0 Lil reagent. inert with respect to the paper, and containing a fixing reagent'therein.

2. A method for treating colored crepe paper, which comprises. passing a sheet of rollers carrying a concentrated solution of a solid reagent, inert with respect to the paper, and containing a fixing reagent therein.

' 3. A. method for treating colored crepe paper, which comprises treating a sheet of the same with a concentrated solution of an inorganic salt, inert with respect to the paper, and a fixing reagent.

4. A method for treating colored crepe paper, which comprises passing a sheet of the same between a pair of rollers carrying a solution of fixing reagent and simultaneously applying thereto a concentrated salt solution, inert with respect to the paper.

5. A method for making non-bleeding colored crepe paper, which comprises treating a sheet of paper with a dye solution and withv a solution of a fixing reagent, with intermediate creping of the sheet.

. 6. A method for making non-bleeding col ored crepe paper,'which comprises treating a sheet of paper with a dye solution and with a solution of a fixing reagent, with intermediate creping of the sheet, the second solution being relatively ineffective to uncrepe the sheet.

7 A method for making non-bleeding colored crepe paper, which comprises treating a sheet of paper with a dye solution and with a solution of a fixing rea ent, with intermediate removal of excess 0 the first solutions and creping of the sheet.

8. A method for making non-bleeding colored crepe paper, which comprises treating a sheet of paper with a dye solution and with solution and then with a concentrated solution containing a solid reagent inert with respect to the paper, and including a fixing reagent, with intermediate creping of thesheet.

10. A method for making non-bleeding colored crepe paper, which comprises successively treating a sheet of paper first with a dye solutionand then with a solution of fixing reagent in an organic solvent, with intermediate creping of the sheet.

11. A- method for making non-bleeding colored crepe paper, which comprises treating a sheet of paper with a dye solution, removing the excess of solution therefrom, creping the sheet, and finally treating the creped sheet with a concentrated aqueous solution of a fixing reagent.

12. A method for making non-bleeding colored crepe paper, which comprises treating a sheet of paper with a dye solution, removing the excess of solution therefrom, creping the sheet, and finally applying a restricted sheet of paper with a dye solution, creping the sheet, drying, and subsequently treating the creped sheet with a fixing reagent.

' 15. A method for making non-bleeding colored crepe paper, which comprises treating the sheet with a dye solution, removin the excess thereof, crepin the sheet, and t ereafter applying a dye xing and fireproofing reagent thereto, in concentrated solution of the combined reagents. I

16. A method for making non-bleeding colored creped paper, which comprises treating and with a solution of a fireproofing reagent.

18. A method for making non-bleeding colored creped paper, which comprises treating a paper sheet with a solution of a dye, by flooding the sheet with a dye solution and effecting contact of the sheet with a solid surface at the point of wetting, removing the excess of solution, creping the sheet, 'flooding the creped sheet with a substantiall nonstretching fixing reagent solution, passing the wet sheet between compression rollers and finally drying.

' 19. A method for making non-bleeding colored creped paper,.which comprises treating a sheet of paper with a solution-of a dye, by flooding, removing any superficial excess, creping the sheet, dr 'ng, and subsequently treatin thesheet wit a fixing reagent.

20. method for making non-bleeding col ored creped paper, which com rises flooding a paper sheet with a solution 0? ing any superficial excess creping the sheet, drying, subsequently floo' ing the sheet with a concentrated solution of fixing reagent, and finally drying.

21. A method for making nombleeding colored creped paper, which comprises treating a sheet of paper with a solution of a dye, by effecting contact of the sheet with a solid surface at the point of wetting, removing any superficial excess, crepin treating the dyed sheet with a solution of fixing reagent by effecting a contact of the sheet with a solid surface at the point of wetting, and finall drying the sheet.

22. A s eet of tissue pa er, characterized by'possessing a cre ed finis and by containing Katanol-O an sodium tungstate within the fibrous structure thereof.

23. As a stage product, a sheet of creped paper containin a dye fixing reagent and-being free from ye.

24. As a stage product a sheet of creped paper containing a d e fixing reagent substantially wholly wit in the fibers of the sheet, and being free from dye.

25. As a stage product a sheet of creped 06 paper containing a dye fixing reagent suba dye, removthe sheet, drying,

stantially wholly within the fibers of the sheet, also a'fireproofing reagent, and being free from dye.

26. As a product of manufacture, colored crepe paper containing the color substance fixed within the cellulosic fibers thereof with the surfaces of the fibers free from substantial coatings of the color substance, and containing fire-proofing material.

Signed by me at Framingham, Massachusetts, this 8th day of November, 1926.

GARDNER ALDEN. 

